EP2177566A1 - Method for production of water-absorbable resin, and water-absorbable resin produced by the method - Google Patents
Method for production of water-absorbable resin, and water-absorbable resin produced by the method Download PDFInfo
- Publication number
- EP2177566A1 EP2177566A1 EP08777792A EP08777792A EP2177566A1 EP 2177566 A1 EP2177566 A1 EP 2177566A1 EP 08777792 A EP08777792 A EP 08777792A EP 08777792 A EP08777792 A EP 08777792A EP 2177566 A1 EP2177566 A1 EP 2177566A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- absorbent resin
- mass
- reaction
- post
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 144
- 239000011347 resin Substances 0.000 title claims abstract description 144
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000002250 absorbent Substances 0.000 claims abstract description 141
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000010521 absorption reaction Methods 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 239000002504 physiological saline solution Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 25
- 230000014759 maintenance of location Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 206010016807 Fluid retention Diseases 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- 206010021639 Incontinence Diseases 0.000 abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 57
- -1 oxetane compound Chemical class 0.000 description 44
- 239000003431 cross linking reagent Substances 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
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- 239000003921 oil Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000010992 reflux Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 238000004821 distillation Methods 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
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- 230000000704 physical effect Effects 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000003209 petroleum derivative Substances 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- SLNCKLVYLZHRKK-UHFFFAOYSA-N 3-ethyl-3-[2-[(3-ethyloxetan-3-yl)methoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCOCC1(CC)COC1 SLNCKLVYLZHRKK-UHFFFAOYSA-N 0.000 description 7
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- 239000000706 filtrate Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- ARTCZOWQELAGLQ-UHFFFAOYSA-N 3-ethyl-3-[2-[2-[2-[(3-ethyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCOCCOCCOCC1(CC)COC1 ARTCZOWQELAGLQ-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- WDYLJSLAWJKROZ-UHFFFAOYSA-N 3-ethyl-3-[2-[2-[(3-ethyloxetan-3-yl)methoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCOCCOCC1(CC)COC1 WDYLJSLAWJKROZ-UHFFFAOYSA-N 0.000 description 2
- MUFYVOBZHINPDE-UHFFFAOYSA-N 3-methyl-3-[2-[(3-methyloxetan-3-yl)methoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(C)COCCOCC1(C)COC1 MUFYVOBZHINPDE-UHFFFAOYSA-N 0.000 description 2
- XGUMRAJAFVCJQQ-UHFFFAOYSA-N 3-methyl-3-[2-[2-[(3-methyloxetan-3-yl)methoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(C)COCCOCCOCC1(C)COC1 XGUMRAJAFVCJQQ-UHFFFAOYSA-N 0.000 description 2
- YKTJTYJDYTXUJV-UHFFFAOYSA-N 3-methyl-3-[2-[2-[2-[(3-methyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(C)COCCOCCOCCOCC1(C)COC1 YKTJTYJDYTXUJV-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- SZYSLWCAWVWFLT-UTGHZIEOSA-N [(2s,3s,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)-2-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxolan-2-yl]methyl octadecanoate Chemical compound O([C@@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@]1(COC(=O)CCCCCCCCCCCCCCCCC)O[C@H](CO)[C@@H](O)[C@@H]1O SZYSLWCAWVWFLT-UTGHZIEOSA-N 0.000 description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
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- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
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- 238000005342 ion exchange Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- 238000006386 neutralization reaction Methods 0.000 description 2
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- 239000012044 organic layer Substances 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- FBNSUSRVIKDLBQ-UHFFFAOYSA-N 3-butyl-3-[2-[2-[(3-butyloxetan-3-yl)methoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CCCC)COCCOCCOCC1(CCCC)COC1 FBNSUSRVIKDLBQ-UHFFFAOYSA-N 0.000 description 1
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- NCSQQHVXSFQOHF-UHFFFAOYSA-N 3-butyl-3-[2-[2-[2-[2-[2-[(3-butyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CCCC)COCCOCCOCCOCCOCCOCC1(CCCC)COC1 NCSQQHVXSFQOHF-UHFFFAOYSA-N 0.000 description 1
- WUGFSEWXAWXRTM-UHFFFAOYSA-N 3-ethyl-3-[2-[2-[2-[2-[(3-ethyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCOCCOCCOCCOCC1(CC)COC1 WUGFSEWXAWXRTM-UHFFFAOYSA-N 0.000 description 1
- ZXOBHNYONVHJMM-UHFFFAOYSA-N 3-ethyl-3-[2-[2-[2-[2-[2-[(3-ethyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCOCCOCCOCCOCCOCC1(CC)COC1 ZXOBHNYONVHJMM-UHFFFAOYSA-N 0.000 description 1
- WJHATQYDHKPODO-UHFFFAOYSA-N 3-methyl-3-[2-[2-[2-[2-[2-[(3-methyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(C)COCCOCCOCCOCCOCCOCC1(C)COC1 WJHATQYDHKPODO-UHFFFAOYSA-N 0.000 description 1
- JQRNFNCRCSRRQR-UHFFFAOYSA-N 3-propan-2-yl-3-[2-[(3-propan-2-yloxetan-3-yl)methoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(C(C)C)COCCOCC1(C(C)C)COC1 JQRNFNCRCSRRQR-UHFFFAOYSA-N 0.000 description 1
- CEEJPTMBAFPILG-UHFFFAOYSA-N 3-propan-2-yl-3-[2-[2-[2-[(3-propan-2-yloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(C(C)C)COCCOCCOCCOCC1(C(C)C)COC1 CEEJPTMBAFPILG-UHFFFAOYSA-N 0.000 description 1
- DIFIYRHNXODGCQ-UHFFFAOYSA-N 3-propan-2-yl-3-[2-[2-[2-[2-[2-[(3-propan-2-yloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(C(C)C)COCCOCCOCCOCCOCCOCC1(C(C)C)COC1 DIFIYRHNXODGCQ-UHFFFAOYSA-N 0.000 description 1
- YGKLYDJPPCMFAB-UHFFFAOYSA-N 3-propyl-3-[2-[(3-propyloxetan-3-yl)methoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CCC)COCCOCC1(CCC)COC1 YGKLYDJPPCMFAB-UHFFFAOYSA-N 0.000 description 1
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- VYVBDSYWMUEAAI-UHFFFAOYSA-N 3-propyl-3-[2-[2-[2-[(3-propyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CCC)COCCOCCOCCOCC1(CCC)COC1 VYVBDSYWMUEAAI-UHFFFAOYSA-N 0.000 description 1
- WNBQNIPCPAILEX-UHFFFAOYSA-N 3-propyl-3-[2-[2-[2-[2-[2-[(3-propyloxetan-3-yl)methoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CCC)COCCOCCOCCOCCOCCOCC1(CCC)COC1 WNBQNIPCPAILEX-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
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- 229920000896 Ethulose Polymers 0.000 description 1
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- 229920001214 Polysorbate 60 Polymers 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
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- 239000012670 alkaline solution Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
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- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
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- 244000309464 bull Species 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- FPNCFEPWJLGURZ-UHFFFAOYSA-L iron(2+);sulfite Chemical compound [Fe+2].[O-]S([O-])=O FPNCFEPWJLGURZ-UHFFFAOYSA-L 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1525—Four-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Definitions
- the present invention relates to a method for producing a water-absorbent resin and a water-absorbent resin obtained by the method. More specifically, the present invention relates to a method for producing a water-absorbent resin which can be preferably used in hygienic materials such as disposable diaper, incontinence pad and sanitary napkin; and a water-absorbent resin obtained by the method.
- a water-absorbent resin has been widely used in hygienic materials such as disposable diaper and sanitary napkin, and industrial materials such as water blocking materials for cables.
- the water-absorbent resin there has been known, for example, hydrolysates of starch-acrylonitrile graftpolymers, neutralized products of starch-acrylate graftpolymers, saponified products of vinyl acetate-acrylic ester copolymers, partially neutralized products of polyacrylic acid, and the like.
- the water-absorbent resin used in hygienic materials is excellent in properties such as water-retention capacity (absorption capacity), water-absorption capacity under load, water-absorption rate, and particle size distribution.
- water-retention capacity absorption capacity
- water-absorption capacity under load absorption capacity under load
- water-absorption rate a method of increasing a crosslinking density on a surface vicinity of the water-absorbent resin
- the water-absorbent resin used in disposable diaper, sanitary napkin and the like is required to have reduced water-soluble substance and to be excellent in safety, besides the above-mentioned properties. For instance, in the case where there is a large amount of the water-soluble substance, the water-soluble substance is eluted after liquid absorption, and slimy liquid is adhered to the skin, thereby causing a possible irritation.
- An object of the present invention is to provide a method for producing a water-absorbent resin which can be preferably used in hygienic materials, which is excellent in properties such as the water-retention capacity and the water-absorption capacity under load, while giving consideration to safety, such as having a reduced water-soluble substance; and a water-absorbent resin obtained by the method.
- a water-absorbent resin which can be preferably used in hygienic materials, which is excellent in properties such as the water-retention capacity and the water-absorption capacity under load, while giving consideration to safety, such as having a reduced water-soluble substance is obtained by evenly crosslinking a surface vicinity of the water-absorbent resin precursor in a high crosslinking density, using a specified crosslinking agent to increase a crosslinking density on a surface vicinity of the water-absorbent resin precursor.
- the present invention relates to:
- R is an alkyl group having 1 to 6 carbon atoms
- n is an integer of from 0 to 6, to a water-absorbent resin precursor obtainable by polymerizing water-soluble ethylenically unsaturated monomers, and subjecting the components to a post-crosslinking reaction while heating; and
- a method for producing a water-absorbent resin which can be preferably used in hygienic materials, which is excellent in properties such as the water-retention capacity and the water-absorption capacity under load, while giving consideration to safety, such as having a reduced water-soluble substance; and a water-absorbent resin obtained by the method.
- Figure 1 is a schematic view of an apparatus for determining absorption capacity of physiological saline under load of the water-absorbent resin.
- a method of polymerizing a water-soluble ethylenically unsaturated monomer to obtain a water-absorbent resin precursor is not particularly limited, and includes an aqueous solution polymerization method, a reversed-phase suspension polymerization method, and the like, which are the representative polymerization methods.
- a reversed-phase suspension polymerization of a water-soluble ethylenically unsaturated monomer in a water-in-oil system is carried out, for example, using a radical polymerization initiator, in a petroleum hydrocarbon medium containing a surfactant and/or a polymeric dispersion agent, with the addition of a crosslinking agent and a chain transfer agent as occasion demands.
- the water-absorbent resin precursor can be obtained by additionally adding the water-soluble ethylenically unsaturated monomer to the water-absorbent resin precursor obtained by the reversed-phase suspension polymerization and carrying out a polymerization in multi-steps of two or more steps.
- the water-soluble ethylenically unsaturated monomer includes, for example, (meth)acrylic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid and alkali metal salts thereof; nonionic unsaturated monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, and N-methylol(meth)acrylamide; amino group-containing unsaturated monomers such as diethylaminoethyl (meth)acrylate and diethylaminopropyl (meth)acrylate, and quaternary compounds thereof; and the like. These may be used alone or in combination of two or more kinds.
- (meth)acryl-" herein means "acryl-" and "methacryl-.”
- (meth)acrylic acid and alkali metal salts thereof (meth)acrylamide, N,N-dimethyl(meth)acrylamide and the like are preferably used, from the viewpoint of being industrially easily available. Further, (meth)acrylic acid and alkali metal salts thereof are more preferably used, from the viewpoint of high water-absorption properties of the resulting water-absorbent resin.
- the water-soluble ethylenically unsaturated monomer can be usually used in the form of an aqueous solution. It is preferably used that the concentration of the water-soluble ethylenically unsaturated monomers in the aqueous solution of the water-soluble ethylenically unsaturated monomers is from 15% by mass to a saturated concentration.
- the acid group may be neutralized with an alkaline neutralizer which comprises an alkali metal salt.
- an alkaline neutralizer which comprises an alkali metal salt.
- the alkali metal salt includes lithium, sodium, potassium, and the like. Among them, sodium and potassium are preferably used, and sodium is more preferably used.
- the radical polymerization initiator includes, for example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, and hydrogen peroxide; azo compounds such as 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(N-phenylamidino)propane]dihydrochloride, 2,2'-azobis[2-(N-allyiamidino)propane]dihydrochloride, 2,2'-azobis ⁇ 2-(1-(2-hydroxyethyl)-2-
- radical polymerization initiators may be used alone or in combination of two or more kinds.
- potassium persulfate, ammonium persulfate, sodium persulfate, and 2,2'-azobis(2-amidinopropane)dihydrochloride are preferably used, from the viewpoint of being industrially easily available and excellent in storage stability.
- the radical polymerization initiator is usually used in each reaction step in an amount of preferably from 0.005 to 1% by mol, based on the amount of the water-soluble ethylenically unsaturated monomer used in each reaction step, from the viewpoint of shortening the time period of the polymerization reaction and preventing a rapid polymerization reaction.
- the above-mentioned radical polymerization initiator can be used as a redox polymerization initiator together with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfite, and L-ascorbic acid.
- a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfite, and L-ascorbic acid.
- the petroleum hydrocarbon medium includes, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and ligroin; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and the like.
- n-hexane, n-heptane, and cyclohexane are preferably used, from the viewpoint of being industrially easily available, stable in quality, and inexpensive.
- These petroleum hydrocarbon mediums may be used alone or may be used in combination of two or more kinds.
- the petroleum hydrocarbon medium is usually contained in an amount of preferably from 50 to 600 parts by mass, and more preferably from 80 to 550 parts by mass, based on the total amount of 100 parts by mass of the water-soluble ethylenically unsaturated monomer in each reaction step, from the viewpoint of removing heat of polymerization and making the polymerization temperature easier to control.
- the surfactant includes, for example, polyglycerol fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerol fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkylallylformaldehyde condensed polyoxyethylene ethers, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, phosphoric esters of polyoxyethylene alkyl ethers, and phosphoric esters of polyoxyethylene alkylallyl ethers.
- the polymeric dispersion agent includes, for example, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified EPDM (ethylene-propylene-diene terpolymer), maleic anhydride-modified polybutadiene, ethylene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, butadiene-maleic anhydride copolymer, oxidized polyethylene, ethylene-acrylic acid copolymer, ethyl cellulose, ethyl hydroxyethyl cellulose, and the like.
- maleic anhydride-modified polyethylene maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, oxidized polyethylene and ethylene-acrylic acid copolymer are preferably used, from the viewpoint of dispersion stability of the aqueous solution of the monomer.
- These polymeric dispersion agents may be used alone or in combination of two or more kinds.
- Each of the surfactant and/or the polymeric dispersion agent is used in an amount of preferably from 0.1 to 5 parts by mass, and more preferably from 0.2 to 3 parts by mass, based on the amount of 100 parts by mass of the aqueous solution of the water-soluble ethylenically unsaturated monomer used in each reaction step, in order to keep an excellent dispersion state of the aqueous solution of the monomer in the petroleum hydrocarbon medium, and to obtain a dispersion stability accounting to the amount used.
- the polymerization reaction can be carried by adding, as an internal crosslinking agent, a compound having a plurality of polymerizable unsaturated groups, and the like, to the water-soluble ethylenically unsaturated monomer.
- the internal crosslinking agent mentioned above includes, for example, unsaturated (poly)esters obtained by reacting polyols such as diols and triols, such as (poly)ethylene glycol [The term "(poly)” means cases where the prefix "poly” is included and where the prefix is not included. In other words, "(poly)" means a polymer compound and a monomer compound.
- unsaturated acid such as (meth)acrylic acid, maleic acid
- a compound having a reactive functional group capable of reacting with a carboxyl group can be used as the other internal crosslinking agents.
- the compound having a reactive functional group capable of reacting with a carboxyl group includes, for example, hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate and hydroxyethyl (meth)acrylate; N-hydroxyalkyl(meth)acrylamides such as N-hydroxymethyl(meth)acrylamide and N-hydroxyethyl(meth)acrylamide; and the like.
- These internal crosslinking agents may be used in combination of two or more kinds.
- the internal crosslinking agent is used in an amount of preferably 1% by mol or less, and more preferably 0.5% by mol or less, based on the amount of the water-soluble ethylenically unsaturated monomer used in each reaction step, from the viewpoint of appropriately crosslinking the resulting water-absorbent resin, thereby suppressing the water solubility of the water-absorbent resin and sufficiently enhancing water-absorption capacity of the resulting resin.
- a chain transfer agent may be added.
- hypophosphites, phosphites, thiols, secondary alcohols, amines and the like can be exemplified.
- the reaction temperature upon the polymerization reaction differs depending upon the radical polymerization initiator used.
- the reaction temperature is preferably from 20° to 110°C and more preferably from 40° to 90°C, from the viewpoint of rapid progress of the polymerization and shortening the polymerization time, thereby increasing productivity and easily removing heat of polymerization, to smoothly carry out the reaction.
- the reaction time is usually from 0.1 to 4 hours.
- Water and the petroleum hydrocarbon medium may be removed from the mixture after the polymerization reaction, for example, by heating the mixture at a temperature of from 80° to 200°C.
- the reversed-phase suspension polymerization is carried out, to give a water-absorbent resin precursor.
- the present invention is characterized by adding a bisoxetane compound as a post-crosslinking agent represented by the following general formula (1):
- R is an alkyl group having 1 to 6 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and the like.
- n is an integer of from 0 to 6.
- bisoxetane compound represented by the formula (1) includes, for example, 1,6-bis(3-methyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-ethyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-n-propyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-isopropyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-n-butyloxetane-3-yl)-2,5-dioxahexane, 1,9-bis(3-methyloxetane-3-yl)-2,5,8-trioxanonane, 1,9-bis(3-ethyloxetane-3-yl)-2,5,8-trioxan
- These bisoxetane compounds may be used alone or in combination of two or more kinds.
- the bisoxetane compound represented by the formula (1) can be prepared by, for example, a method of reacting a sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane and a diol compound in the presence of a base (Japanese Patent Laid-Open No. 2000-302774 , and Japanese Patent Laid-Open No. 2000-319577 ), a method of reacting 3-alkyl-3-hydroxymethyloxetane and an ⁇ , ⁇ -dihaloalkane in the presence of an alkaline solution using a phase-transfer catalyst ( Pure Appl. Chem., A30 (2&3), pp.189 (1993 ); and Bull. Chem. Soc. Jpn., 61 1653-1659 (1988 )), and the like.
- the amount of the bisoxetane compound used cannot be absolutely determined since the amount varies with the kind of the compound used.
- the bisoxetane compound is usually used in an amount of preferably from 0.001 to 3% by mol, more preferably from 0.01 to 2% by mol, and still more preferably from 0.1 to 1% by mol, based on the total amount of the water-soluble ethylenically unsaturated monomer used to obtain the water-absorbent resin precursor, from the viewpoint of sufficiently increasing the crosslinking density in a surface vicinity of the water-absorbent resin thereby enhancing the properties such as the water-absorption capacity under load, and from the viewpoint of preventing excess crosslinking reactions thereby enhancing the water-retention capacity.
- the post-crosslinking agent including the bisoxetane compound is preferably used by dissolving in a solvent.
- the type of solvent includes water; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol; ketones such as acetone, and methyl ethyl ketone; and the like. These solvents may be used alone or in combination of two or more kinds. Among them, water and alcohols are preferably used.
- the above-mentioned solvent is used in an amount of preferably from 1 to 50 parts by mass, more preferably from 1 to 40 parts by mass, and still more preferably from 5 to 40 parts by mass, based on 100 parts by mass of the water-absorbent resin precursor.
- the timing for adding the post-crosslinking agent including the bisoxetane compound is not particularly limited, as long as the timing is after the water-absorbent resin precursor is obtained by polymerizing the water-soluble ethylenically unsaturated monomer.
- the post-crosslinking agent is added to the water-absorbent resin precursor, and thereafter, for example, the post-crosslinking reaction is carried out while distilling off water and/or a petroleum hydrocarbon medium by heating, whereby the water-absorbent resin of the present invention can be obtained.
- the water content of the water-absorbent resin precursor immediately prior to adding the post-crosslinking agent is preferably 65% by mass or less, more preferably from 1 to 50% by mass or less, still more preferably from 5 to 50% by mass or less, and still more preferably from 5 to 33% by mass or less.
- the "water content” is the value determined by the determination method described below.
- a surface vicinity of the water-absorbent resin precursor can be crosslinked.
- the temperature for the above-mentioned heating is preferably from 50° to 200°C, and more preferably from 80° to 180°C, from the viewpoint of rapidly and evenly crosslinking a surface vicinity of the water-absorbent resin thereby enhancing the properties such as the water-retention capacity and the water-absorption capacity under load, and from the viewpoint of preventing decomposition or degradation of the water-absorbent resin.
- the reaction time is preferably 0.1 to 5 hours, and preferably 0.5 to 4 hours.
- reaction aid in order to keep the reaction temperature low and shortening the reaction time during the post-crosslinking reaction.
- reaction aid proton acid and Lewis acid are preferably used.
- inorganic acids such as sulfuric acid, phosphoric acid and hydrochloric acid
- organic acids such as citric acid, glyoxylic acid, glycolic acid, glutaric acid, cinnamic acid, succinic acid, and lactic acid; and the like are preferably used.
- phosphoric acid and lactic acid are more preferably used.
- the amount of the reaction aid used cannot be absolutely determined since the amount varies with the kind of the compound used, reaction conditions and the like.
- the reaction aid is desirably 0.0001 to 5-fold the amount of the bisoxetane compound on the molar basis.
- An additive such as a lubricant, a deodorizing agent or an antimicrobial agent may be further added to the water-absorbent resin of the present invention depending upon its purpose.
- the water-absorbent resin obtained by the production method of the present invention has a retention capacity of physiological saline of 30 g/g or more, an absorption capacity of physiological saline under a load of 2.07 kPa of 15 mL/g or more, and has a water-soluble substance of 20% by mass or less. Since the water-absorbent resin obtained by the method of the present invention is excellent in properties such as water-retention capacity, and water-absorption capacity under load, and also gives consideration to safety of the water-absorbent resin by reducing water-soluble substance, the water-absorbent resin can be preferably used in hygienic materials.
- retention capacity of physiological saline is the values determined according to the determination method described as set forth below.
- the water-absorbent resin of the present invention has a retention capacity of physiological saline of preferably 30 g/g or more, more preferably 35 g/g or more, even more preferably 40 g/g or more, and even more preferably from 40 to 70 g/g, from the viewpoint of, upon being used in a hygienic material, increasing absorption capacity and lowering the amount of re-wet of liquid.
- the water-absorbent resin of the present invention has an absorption capacity of physiological saline under a load of 2.07 kPa of preferably 15 mL/g or more, more preferably 17 mL/g or more, even more preferably 20 mL/g or more, and even more preferably from 20 to 45 mL/g, from the viewpoint of, upon being used as a hygienic material, lowering the amount of re-wet of liquid in a case where pressure is applied to the hygienic material after liquid absorption.
- the water-absorbent resin of the present invention has a water-soluble substance of preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of, upon being used in a hygienic material, preventing adhesion of the slimy liquid to the skin.
- a water-absorbent resin precursor is obtained by polymerizing a water-soluble ethylenically unsaturated monomer, and thereafter, a bisoxetane compound is added thereto as a crosslinking agent, to carry out a post-crosslinking reaction, whereby a water-absorbent resin which is excellent in properties such as water-retention capacity, and water-absorption capacity under load, while giving consideration to safety for the human body by reducing water-soluble substance, can be obtained.
- the reason why the water-absorbent resin having excellent properties and reduced water-soluble substance as above-mentioned can be obtained is not clear. Although not wanting to be limited by theory, the reason can be presumed as follows. Briefly, it is considered that the reason is due to the fact that, a water-absorbent resin precursor is reacted in the presence of a bisoxetane compound as a post-crosslinking agent, whereby a reaction of a carboxyl group and an oxetane group in the water-absorbent resin proceeds in an appropriate rate, so that a surface vicinity of the water-absorbent resin can be evenly crosslinked in a high crosslinking density.
- the bisoxetane compound described herein has a glycol chain in its molecule thereby being excellent in water solubility, so that the compound is excellent in an even dispersion upon being added to the water-absorbent resin precursor, or in compatibility with the precursor, thereby making it possible to crosslink the surface vicinity more evenly.
- the amount 2.0 g of water-absorbent resin were weighed in a cotton bag (Cottonbroad No. 60, width 100 mm ⁇ length 200 mm), and placed in a 500 ml-beaker.
- Physiological saline (0.9% by mass aqueous solution of sodium chloride, hereinafter referred to the same) was poured into the cotton bag in an amount of 500 g at one time, and the physiological saline was dispersed so as not to generate an unswollen lump of the water-absorbent resin.
- the upper part of the cotton bag was tied up with a rubber band, and the cotton bag was allowed to stand for 1 hour, to sufficiently swell the water-absorbent resin.
- the cotton bag was dehydrated for 1 minute with a dehydrator (manufactured by Kokusan Enshinki Co., Ltd., product number: H-122) set to have a centrifugal force of 167G.
- the mass Wa (g) of the cotton bag containing swollen gels after the dehydration was determined.
- the same procedures were carried out without adding water-absorbent resin, and the empty mass Wb (g) of the cotton bag upon wetting was determined.
- the apparatus X shown in Figure 1 comprises a buret section 1, a lead tube 2, a measuring board 3, and a measuring section 4 placed on the measuring board 3.
- a rubber plug 14 on the top of a buret 10 To the buret section 1 are connected a rubber plug 14 on the top of a buret 10, and an air introduction tube 11 and a cock 12 at the bottom portion of the buret 10, and further, the air introduction tube 11 has a cock 13 at the end.
- the lead tube 2 is attached between the buret section 1 and the measuring board 3.
- the lead tube 2 has an inner diameter of 6 mm.
- a hole of a diameter of 2 mm is made at the central section of the measuring board 3, and the lead tube 2 is connected thereto.
- the measuring section 4 has a cylinder 40, a nylon mesh 41 adhered to the bottom part of the cylinder 40, and a weight 42.
- the cylinder 40 has an inner diameter of 2.0 cm.
- the nylon mesh 41 has an opening of 200 mesh (75 ⁇ m), and is configured so as a predetermined amount of the water-absorbent resin 5 to be evenly spread over the nylon mesh 41.
- the weight 42 has a diameter of 1.9 cm and a mass of 59.8 g. This weight 42 is placed on the water-absorbent resin 5, so that a 2.07 kPa load can be applied to the water-absorbent resin 5.
- the cock 12 and the cock 13 at the buret section 1 are closed, and a physiological saline adjusted to 25°C is poured from the top of the buret 10 and the top of the buret is plugged with the rubber plug 14. Thereafter, the cock 12 and the cock 13 at the buret section 1 are opened. Next, the height of the measuring board 3 is adjusted so that the end of the lead tube 2 in the central section of the measuring board 3 and an air introduction port of the air introduction tube 11 are at the same height.
- the water-absorbent resin 5 is evenly spread over the nylon mesh 41 in the cylinder 40, and the weight 42 is placed on the water-absorbent resin 5.
- the measuring section 4 is placed so that its central section is in alignment with a lead tube port in the central section of the measuring board 3.
- the absorption capacity of physiological saline under load of the water-absorbent resin 5 after 60 minutes passed from a time point of starting water absorption was obtained by the following formula.
- Absorption Capacity of Physioligical Saline Under Load ml / g Wc ml / 0.10 g
- the amount 500 ⁇ 0.1 g of physiological saline was weighed out in a 500 ml-beaker.
- a magnetic stirrer bar (8 mm ⁇ ⁇ 30 mm, ringless) was placed therein, and the beaker was placed on a magnetic stirrer (HS-30D, manufactured by iuchi). Subsequently, the magnetic stirrer bar was adjusted so as to rotate at a rate of 600 r/min. In addition, a bottom of a vortex generated by rotation of the magnetic stirrer bar was adjusted so as to be near an upper portion of the magnetic stirrer bar.
- the amount 80 ⁇ 0.0005 g of the resulting filtrate was weighed out in a 100 ml-beaker adjusted to a constant weight.
- the filtrate was dried with a forced convection oven (FV-320, manufactured by ADVANTEC) set at an internal temperature of 140°C until a constant weight was attained, and a mass Wd (g) of the solid content of the filtrate was determined.
- FV-320 forced convection oven
- JIS standard sieves a sieve having an opening of 850 ⁇ m, a sieve having an opening of 600 ⁇ m, a sieve having an opening of 425 ⁇ m, a sieve having an opening of 300 ⁇ m, a sieve having an opening of 150 ⁇ m, a sieve having an opening of 75 ⁇ m, and a receiving tray were combined in order from the top.
- About 100 g of the water-absorbent resin was placed on an uppermost sieve, and shaken for 20 minutes with a rotating and tapping shaker machine.
- a particle diameter corresponding to a 50% cumulative mass percentage is defined as an average particle diameter by joining the plots on the probability paper in a straight line.
- the amount 2.0 g of the water-absorbent resin (water-absorbent resin precursor) was precisely weighed out (Wg (g)) in an aluminum foil case (No. 8) of which constant weight (Wf (g)) was previously attained.
- the above sample was dried for 2 hours with a forced convection oven (manufactured by ADVANTEC) set at an internal temperature of 105°C. Thereafter, the dried sample was allowed to be cooled in a desiccator, and a mass Wh (g) after drying was determined.
- a 1-liter four-neck flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube was charged with 44.1 g (0.38 mol) of 3-ethyl-3-hydroxymethyloxetane, 44.6 g (0.44 mol) of triethylamine and 220 g of toluene.
- the contents were externally cooled in an ice-water bath until the internal temperature was 5°C under a nitrogen gas atmosphere.
- 45.8 g (0.4 mol) of methanesulfonyl chloride was added dropwise so as the internal temperature not to exceed 10°C.
- the above reaction filtrate was returned to the flask, and 6.4 g (0.02 mol) of tetra-n-butylammonium bromide as a catalyst and 13.7 g (0.22 mol) of ethylene glycol were added thereto.
- the contents were heated to the internal temperature of 60°C, and thereafter 12 g (0.3 mol) of sodium hydroxide in a pellet form was added under stirring over a period of 1 hour. Subsequently, the contents were reacted at the same temperature for 2 hours, and the internal temperature was then raised to 70°C and the reaction was allowed to proceed for 5 hours.
- a 2-liter four-neck flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube was charged with 672 g (8.4 mol) of 50% by mass aqueous solution of sodium hydroxide, 25.5 g (0.075 mol) of tetra-n-butylammonium hydrogensulfate, and 330 g of n-hexane.
- the contents were heated in an oil bath until the internal temperature was 65°C under a nitrogen gas atmosphere.
- 58.1 g (0.5 mol) of 3-ethyl-3-hydroxymethyloxetane was added dropwise, and stirred at the same temperature for 30 minutes.
- the reaction solution was transferred to a separatory funnel to allow phase separation, and the resulting organic layer was distilled in a reduced-distillation apparatus at an oil bath temperature of 250°C and a reduced pressure degree of 3 mmHg, to give 38.1 g of a target 1,12-bis(3-ethyloxetane-3-yl)-2,5,8,11-tetraoxadodecane (0.11 mol, yield:22%, purity 94%).
- the purity was determined from the peak area ratio in the chart obtained from gas chromatography.
- a cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube and a stirring blade was prepared. This flask was charged with 340 g of n-heptane, and 0.92 g of a sucrose stearate having an HLB of 3 (manufactured by Mitsubishi-Kagaku Foods Corporation, Ryoto sugar ester S-370) and 0.92 g of a maleic anhydride-modified ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Inc., Hi-wax 1105A) were added thereto. The temperature was raised to 80°C while stirring, to dissolve the surfactant, and thereafter the solution was cooled to 50°C.
- a 500 ml-Erlenmeyer flask was charged with 92 g (1.02 mol) of an 80% by mass aqueous solution of acrylic acid, and 146.0 g of a 21% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.11 g (0.41 mmol) of potassium persulfate and 9.2 mg (0.06 mmol) of N,N'-methylenebisacrylamide were added thereto to dissolve, to prepare an aqueous monomer solution for the first step.
- this aqueous monomer solution for the first step was added to the above separable flask, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was immersed in a water bath at 70°C to raise the temperature, and the first-step polymerization was carried out for 1 hour and then cooled to a room temperature, to give a polymerization slurry of the first step.
- an another 500 ml-Erlenmeyer flask was charged with 128.8 g (1.43 mol) of an 80% by mass aqueous solution of acrylic acid, and 159.0 g of a 27% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.16 g (0.59 mmol) of potassium persulfate and 12.9 mg (0.08 mmol) of N,N'-methylenebisacrylamide were added thereto to dissolve, to prepare an aqueous monomer solution for the second step.
- this aqueous monomer solution for the second step was added to the above slurry after polymerization, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was again immersed in a water bath at 70°C to raise the temperature, and the second-step polymerization was carried out.
- the reaction mixture was heated with an oil bath at 125°C, whereby only water was removed from the azeotropic mixture of n-heptane and water. Further, n-heptane in the internal of the system was removed by distillation, to give 237.5 g of the water-absorbent resin precursor (A1), which is an aggregate of spherical particles and has an average particle size of 359 ⁇ m.
- the water-absorbent resin precursor at this point had a drying loss (water content) of 7.1% by mass.
- a cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube and a stirring blade was prepared. This flask was charged with 340 g of n-heptane, and 0.92 g of a sucrose stearate having an HLB of 3 (manufactured by Mitsubishi-Kagaku Foods Corporation, Ryoto sugar ester S-370) and 0.92 g of a maleic anhydride-modified ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Inc., Hi-wax 1105A) were added thereto. The temperature was raised to 80°C while stirring, to dissolve the surfactant, and thereafter the solution was cooled to 50°C.
- a 500 ml-Erlenmeyer flask was charged with 92 g (1.02 mol) of an 80% by mass aqueous solution of acrylic acid, and 146.0 g of a 21% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.11 g (0.41 mmol) of potassium persulfate as a radical polymerization initiator and 9.2 mg (0.06 mmol) of N,N'-methylenebisacrylamide as an internal-crosslinking agent were added thereto to dissolve, to prepare an aqueous monomer solution for the first step.
- this aqueous monomer solution for the first step was added to the above separable flask, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was immersed in a water bath at 70°C to raise the temperature, and the first-step polymerization was carried out and then cooled to a room temperature, to give a polymerization slurry of the first step.
- an another 500 ml-Erlenmeyer flask was charged with 128.8 g (1.43 mol) of an 80% by mass aqueous solution of acrylic acid, and 159.0 g of a 27% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.16 g (0.59 mmol) of potassium persulfate as a radical polymerization initiator and 12.9 mg (0.08 mmol) of N,N'-methylenebisacrylamide as an internal-crosslinking agent were added thereto to dissolve, to prepare an aqueous monomer solution for the second step.
- this aqueous monomer solution for the second step was added to the above slurry after polymerization, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was again immersed in a water bath at 70°C to raise the temperature, and the second-step polymerization was carried out.
- the temperature of the reaction solution was raised in an oil bath at 125°C, and 260 g of water was removed outside the system while refluxing n-heptane by azeotropic distillation of n-heptane and water, to give 266 g of the water-absorbent resin (A2) (water content: 18.3% by mass.).
- the internal temperature was raised to 80°C. Thereafter, 5.0 g of a 10% by mass aqueous solution of 1,4-butanediol (5.5 mmol) was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 2 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 2.0% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- the internal temperature was raised to 80°C. Thereafter, 5.0 g of a 10% by mass aqueous solution of 3-methyl-3-oxetanemethanol (4.9 mmol) was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 2 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 3.2% by mass.
- the physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- the internal temperature was raised to 80°C. Thereafter, 16.7 g of a 3% by mass aqueous solution of di[1-ethyl(3-oxetanyl)]methyl ether (2.3 mmol) was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 2 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 2.2% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- the water-absorbent resin obtained by the method for producing a water-absorbent resin of the present invention is excellent in properties such as water-retention capacity, and water-absorption capacity under load, and also gives consideration to safety of the water-absorbent resin by reducing water-soluble substance. Therefore, the water-absorbent resin of the present invention can be preferably used, for example, in hygienic materials such as disposable diaper, incontinence pad and sanitary napkin, in particular, in disposable diaper.
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Abstract
to a water-absorbent resin precursor obtainable by polymerizing water-soluble ethylenically unsaturated monomers, and subjecting the components to a post-crosslinking reaction while heating; and a water-absorbent resin obtainable by the method, characterized in that the water-absorbent resin has a retention capacity of physiological saline of 30 g/g or more, an absorption capacity of physiological saline under a load of 2.07 kPa of 15 ml/g or more, and a water-soluble substance of 20% by mass or less. The water-absorbent resin obtained by the method of the present invention is excellent in properties such as water-retention capacity, and water-absorption capacity under load, and also gives consideration to safety of the water-absorbent resin by reducing water-soluble substance. Therefore, the water-absorbent resin of the present invention can be preferably used, for example, in hygienic materials such as disposable diaper, incontinence pad and sanitary napkin, in particular, in disposable diaper.
Description
- The present invention relates to a method for producing a water-absorbent resin and a water-absorbent resin obtained by the method. More specifically, the present invention relates to a method for producing a water-absorbent resin which can be preferably used in hygienic materials such as disposable diaper, incontinence pad and sanitary napkin; and a water-absorbent resin obtained by the method.
- Conventionally, a water-absorbent resin has been widely used in hygienic materials such as disposable diaper and sanitary napkin, and industrial materials such as water blocking materials for cables. As the water-absorbent resin, there has been known, for example, hydrolysates of starch-acrylonitrile graftpolymers, neutralized products of starch-acrylate graftpolymers, saponified products of vinyl acetate-acrylic ester copolymers, partially neutralized products of polyacrylic acid, and the like.
- Among them, it has been desired that the water-absorbent resin used in hygienic materials is excellent in properties such as water-retention capacity (absorption capacity), water-absorption capacity under load, water-absorption rate, and particle size distribution. In the past, in order to improve particularly the water-retention capacity and the water-absorption capacity under load of the above-mentioned properties, there is proposed a method of increasing a crosslinking density on a surface vicinity of the water-absorbent resin (post-crosslinking method).
- Also, the water-absorbent resin used in disposable diaper, sanitary napkin and the like is required to have reduced water-soluble substance and to be excellent in safety, besides the above-mentioned properties. For instance, in the case where there is a large amount of the water-soluble substance, the water-soluble substance is eluted after liquid absorption, and slimy liquid is adhered to the skin, thereby causing a possible irritation.
- In reply to such demands, as a method for improving the above-mentioned properties (in particular, the water-retention capacity and the water-absorption capacity under load) while giving consideration to safety, for example, there has been suggested a method of increasing a crosslinking density on a surface vicinity of the water-absorbent resin, according to a method including the step of mixing with an oxetane compound and a water-soluble additive (see
Patent Publications 1 and 2), a method including the steps of mixing with a ketal compound or an acetal compound and heat-treating the mixture (see Patent Publication 3), a method including the steps of mixing with a specified oxazoline compound and treating the mixture (see Patent Publication 4), or the like. However, even with these technologies, the above-mentioned properties have not yet been satisfactory enough. - Therefore, there has been desired the development of a water-absorbent resin which is excellent in the properties such as the water-retention capacity and the water-absorption capacity under load, while giving consideration to safety, such as having a reduced water-soluble substance.
- Patent Publication 1: Japanese Patent Laid-Open No.
2002-194239 - Patent Publication 2: Japanese Patent Laid-Open No.
2003-313446 - Patent Publication 3: Japanese Patent Laid-Open No.
Hei 08-027278 - Patent Publication 4: Japanese Patent Laid-Open No.
2000-197818 - An object of the present invention is to provide a method for producing a water-absorbent resin which can be preferably used in hygienic materials, which is excellent in properties such as the water-retention capacity and the water-absorption capacity under load, while giving consideration to safety, such as having a reduced water-soluble substance; and a water-absorbent resin obtained by the method.
- The present inventors have found that a water-absorbent resin which can be preferably used in hygienic materials, which is excellent in properties such as the water-retention capacity and the water-absorption capacity under load, while giving consideration to safety, such as having a reduced water-soluble substance is obtained by evenly crosslinking a surface vicinity of the water-absorbent resin precursor in a high crosslinking density, using a specified crosslinking agent to increase a crosslinking density on a surface vicinity of the water-absorbent resin precursor.
- Specifically, the present invention relates to:
- [1] a method for producing a water-absorbent resin, characterized by adding a bisoxetane compound represented by the following general formula (1):
-
- wherein R is an alkyl group having 1 to 6 carbon atoms; and n is an integer of from 0 to 6,
to a water-absorbent resin precursor obtainable by polymerizing water-soluble ethylenically unsaturated monomers, and subjecting the components to a post-crosslinking reaction while heating; and - [2] a water-absorbent resin obtainable by the above method [1], characterized in that the water-absorbent resin has a retention capacity of physiological saline of 30 g/g or more, an absorption capacity of physiological saline under a load of 2.07 kPa of 15 ml/g or more, and a water-soluble substance of 20% by mass or less.
- According to the present invention, there is provided a method for producing a water-absorbent resin which can be preferably used in hygienic materials, which is excellent in properties such as the water-retention capacity and the water-absorption capacity under load, while giving consideration to safety, such as having a reduced water-soluble substance; and a water-absorbent resin obtained by the method.
- [
Figure 1] Figure 1 is a schematic view of an apparatus for determining absorption capacity of physiological saline under load of the water-absorbent resin. -
- X
- determination apparatus
- 1
- buret section
- 10
- buret
- 11
- air introduction tube
- 12
- cock
- 13
- cock
- 14
- rubber plug
- 2
- lead tube
- 3
- measuring board
- 4
- measuring section
- 40
- cylinder
- 41
- nylon mesh
- 42
- weight
- 5
- water-absorbent resin
- In the present invention, a method of polymerizing a water-soluble ethylenically unsaturated monomer to obtain a water-absorbent resin precursor is not particularly limited, and includes an aqueous solution polymerization method, a reversed-phase suspension polymerization method, and the like, which are the representative polymerization methods.
- In the present specification, as one example of the embodiments, the reversed-phase suspension polymerization method is explained in more detail. In the above-mentioned method, a reversed-phase suspension polymerization of a water-soluble ethylenically unsaturated monomer in a water-in-oil system is carried out, for example, using a radical polymerization initiator, in a petroleum hydrocarbon medium containing a surfactant and/or a polymeric dispersion agent, with the addition of a crosslinking agent and a chain transfer agent as occasion demands. Incidentally, in the above-mentioned reversed-phase suspension polymerization method, the water-absorbent resin precursor can be obtained by additionally adding the water-soluble ethylenically unsaturated monomer to the water-absorbent resin precursor obtained by the reversed-phase suspension polymerization and carrying out a polymerization in multi-steps of two or more steps.
- The water-soluble ethylenically unsaturated monomer includes, for example, (meth)acrylic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid and alkali metal salts thereof; nonionic unsaturated monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, and N-methylol(meth)acrylamide; amino group-containing unsaturated monomers such as diethylaminoethyl (meth)acrylate and diethylaminopropyl (meth)acrylate, and quaternary compounds thereof; and the like. These may be used alone or in combination of two or more kinds. Here, "(meth)acryl-" herein means "acryl-" and "methacryl-."
- Among the above-mentioned water-soluble ethylenically unsaturated monomers, (meth)acrylic acid and alkali metal salts thereof, (meth)acrylamide, N,N-dimethyl(meth)acrylamide and the like are preferably used, from the viewpoint of being industrially easily available. Further, (meth)acrylic acid and alkali metal salts thereof are more preferably used, from the viewpoint of high water-absorption properties of the resulting water-absorbent resin.
- The water-soluble ethylenically unsaturated monomer can be usually used in the form of an aqueous solution. It is preferably used that the concentration of the water-soluble ethylenically unsaturated monomers in the aqueous solution of the water-soluble ethylenically unsaturated monomers is from 15% by mass to a saturated concentration.
- In the aqueous solution of the water-soluble ethylenically unsaturated monomer, when the water-soluble ethylenically unsaturated monomer used contains an acid group, the acid group may be neutralized with an alkaline neutralizer which comprises an alkali metal salt. It is preferably used that the degree of neutralization by the above-mentioned alkaline neutralizer is from 10 to 100% by mol of the acid group of the water-soluble ethylenically unsaturated monomer before the neutralization, from the viewpoint of increasing osmotic pressure and not causing any disadvantages in safety or the like due to the presence of an excess alkaline neutralizer. The alkali metal salt includes lithium, sodium, potassium, and the like. Among them, sodium and potassium are preferably used, and sodium is more preferably used.
- The radical polymerization initiator includes, for example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, and hydrogen peroxide; azo compounds such as 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(N-phenylamidino)propane]dihydrochloride, 2,2'-azobis[2-(N-allyiamidino)propane]dihydrochloride, 2,2'-azobis{2-(1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], and 4,4'-azobis(4-cyanovaleric acid); and the like. These radical polymerization initiators may be used alone or in combination of two or more kinds. Among them, potassium persulfate, ammonium persulfate, sodium persulfate, and 2,2'-azobis(2-amidinopropane)dihydrochloride are preferably used, from the viewpoint of being industrially easily available and excellent in storage stability.
- The radical polymerization initiator is usually used in each reaction step in an amount of preferably from 0.005 to 1% by mol, based on the amount of the water-soluble ethylenically unsaturated monomer used in each reaction step, from the viewpoint of shortening the time period of the polymerization reaction and preventing a rapid polymerization reaction.
- The above-mentioned radical polymerization initiator can be used as a redox polymerization initiator together with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfite, and L-ascorbic acid.
- The petroleum hydrocarbon medium includes, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and ligroin; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and the like. Among them, n-hexane, n-heptane, and cyclohexane are preferably used, from the viewpoint of being industrially easily available, stable in quality, and inexpensive. These petroleum hydrocarbon mediums may be used alone or may be used in combination of two or more kinds.
- The petroleum hydrocarbon medium is usually contained in an amount of preferably from 50 to 600 parts by mass, and more preferably from 80 to 550 parts by mass, based on the total amount of 100 parts by mass of the water-soluble ethylenically unsaturated monomer in each reaction step, from the viewpoint of removing heat of polymerization and making the polymerization temperature easier to control.
- The surfactant includes, for example, polyglycerol fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerol fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkylallylformaldehyde condensed polyoxyethylene ethers, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, phosphoric esters of polyoxyethylene alkyl ethers, and phosphoric esters of polyoxyethylene alkylallyl ethers. Among them, sorbitan fatty acid esters, polyglycerol fatty acid esters and sucrose fatty acid esters are preferably used. These surfactants may be used alone or in combination of two or more kinds.
- The polymeric dispersion agent includes, for example, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified EPDM (ethylene-propylene-diene terpolymer), maleic anhydride-modified polybutadiene, ethylene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, butadiene-maleic anhydride copolymer, oxidized polyethylene, ethylene-acrylic acid copolymer, ethyl cellulose, ethyl hydroxyethyl cellulose, and the like. Among them, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, oxidized polyethylene and ethylene-acrylic acid copolymer are preferably used, from the viewpoint of dispersion stability of the aqueous solution of the monomer. These polymeric dispersion agents may be used alone or in combination of two or more kinds.
- Each of the surfactant and/or the polymeric dispersion agent is used in an amount of preferably from 0.1 to 5 parts by mass, and more preferably from 0.2 to 3 parts by mass, based on the amount of 100 parts by mass of the aqueous solution of the water-soluble ethylenically unsaturated monomer used in each reaction step, in order to keep an excellent dispersion state of the aqueous solution of the monomer in the petroleum hydrocarbon medium, and to obtain a dispersion stability accounting to the amount used.
- In the present invention, the polymerization reaction can be carried by adding, as an internal crosslinking agent, a compound having a plurality of polymerizable unsaturated groups, and the like, to the water-soluble ethylenically unsaturated monomer. The internal crosslinking agent mentioned above includes, for example, unsaturated (poly)esters obtained by reacting polyols such as diols and triols, such as (poly)ethylene glycol [The term "(poly)" means cases where the prefix "poly" is included and where the prefix is not included. In other words, "(poly)" means a polymer compound and a monomer compound. Hereinafter referred to the same], (poly)propylene glycol, 1,4-butanediol, trimethylolpropane, polyoxyethylene glycol, polyoxypropylene glycol, or (poly)glycerol with an unsaturated acid such as (meth)acrylic acid, maleic acid or fumaric acid; bisacrylamides such as N,N'-methylenebisacrylamide; di- or tri(meth)acrylate esters obtained by reacting a polyepoxide with (meth)acrylic acid; carbamyl esters of di(meth)acrylic acid obtained by reacting a polyisocyanate such as tolylene diisocyanate or hexamethylene diisocyanate with hydroxyethyl (meth)acrylate; allylated starch, allylated cellulose, diallyl phthalate, N,N',N"-triallyl isocyanurate, divinylbenzene, and the like.
- In addition, as the other internal crosslinking agents, a compound having a reactive functional group capable of reacting with a carboxyl group can be used. The compound having a reactive functional group capable of reacting with a carboxyl group includes, for example, hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate and hydroxyethyl (meth)acrylate; N-hydroxyalkyl(meth)acrylamides such as N-hydroxymethyl(meth)acrylamide and N-hydroxyethyl(meth)acrylamide; and the like.
- These internal crosslinking agents may be used in combination of two or more kinds.
- The internal crosslinking agent is used in an amount of preferably 1% by mol or less, and more preferably 0.5% by mol or less, based on the amount of the water-soluble ethylenically unsaturated monomer used in each reaction step, from the viewpoint of appropriately crosslinking the resulting water-absorbent resin, thereby suppressing the water solubility of the water-absorbent resin and sufficiently enhancing water-absorption capacity of the resulting resin.
- In addition, in order to control water-absorption properties of the water-absorbent resin, a chain transfer agent may be added. As the above-mentioned chain transfer agent, hypophosphites, phosphites, thiols, secondary alcohols, amines and the like can be exemplified.
- The reaction temperature upon the polymerization reaction differs depending upon the radical polymerization initiator used. The reaction temperature is preferably from 20° to 110°C and more preferably from 40° to 90°C, from the viewpoint of rapid progress of the polymerization and shortening the polymerization time, thereby increasing productivity and easily removing heat of polymerization, to smoothly carry out the reaction. The reaction time is usually from 0.1 to 4 hours.
- Water and the petroleum hydrocarbon medium may be removed from the mixture after the polymerization reaction, for example, by heating the mixture at a temperature of from 80° to 200°C.
- As described above, the reversed-phase suspension polymerization is carried out, to give a water-absorbent resin precursor.
- The present invention is characterized by adding a bisoxetane compound as a post-crosslinking agent represented by the following general formula (1):
-
- to the above-mentioned water-absorbent resin precursor, and subjecting the components to a post-crosslinking reaction while heating.
- In the formula (1), R is an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and the like.
- In the formula (1), n is an integer of from 0 to 6.
- Specific examples of the bisoxetane compound represented by the formula (1) includes, for example, 1,6-bis(3-methyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-ethyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-n-propyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-isopropyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-n-butyloxetane-3-yl)-2,5-dioxahexane, 1,9-bis(3-methyloxetane-3-yl)-2,5,8-trioxanonane, 1,9-bis(3-ethyloxetane-3-yl)-2,5,8-trioxanonane, 1,9-bis(3-n-propyloxetane-3-yl)-2,5,8-trioxanonane, 1,9-bis(3-isopropyloxeiane-3-yl)-2,5,8-trioxanonane, 1,9-bis(3-n-butyloxetane-3-yl)-2,5,8-trioxanonane, 1,12-bis(3-methyloxetane-3-yl)-2,5,8,11-tetraoxadodecane, 1,12-bis(3-ethyloxetane-3-yl)-2,5,8,11-tetraoxadodecane, 1,12-bis(3-n-propyloxetane-3-yl)-2,5,8,11-tetraoxadodecane, 1,12-bis(3-isopropyloxetane-3-yl)-2,5,8,11-tetraoxadodecane, 1,12-bis(3-n-butyloxetane-3-yl)-2,5,8,11-tetraoxadodecane, 1,15-bis(3-methyloxetane-3-yl)-2,5,8,11,14-pentaoxapentadecane, 1,15-bis(3-ethyloxetane-3-yl)-2,5,8,11,14-pentaoxapentadecane, 1,15-bis(3-n-propyloxetane-3-yl)-2,5,8,11,14-pentaoxapentadecane, 1,15-bis(3-isopropyloxetane-3-yl)-2,5,8,11,14-pentaoxapentadecane, 1,15-bis(3-n-butyloxetane-3-yl)-2,5,8,11,14-pentaoxapentadecane, 1,18-bis(3-methyloxetane-3-yl)-2,5,8,11,14,17-hexaoxaoctadecane, 1,18-bis(3-ethyloxetane-3-yl)-2,5,8,11,14,17-hexaoxaoctadecane, 1,18-bis(3-n-propyloxetane-3-yl)-2,5,8,11,14,17-hexaoxaoctadecane, 1,18-bis(3-isopropyloxetane-3-yl)-2,5,8,11,14,17-hexaoxaoctadecane, 1,18-bis(3-n-butyloxetane-3-yl)-2,5,8,11,14,17-hexaoxaoctadecane, and the like. Among them, 1,6-bis(3-methyloxetane-3-yl)-2,5-dioxahexane, 1,6-bis(3-ethyloxetane-3-yl)-2,5-dioxahexane, 1,9-bis(3-methyloxetane-3-yl)-2,5,8-trioxanonane, 1,9-bis(3-ethyloxetane-3-yl)-2,5,8-trioxanonane, 1,12-bis(3-methyloxetane-3-yl)-2,5,8,11-tetraoxadodecane, and 1,12-bis(3-ethyloxetane-3-yl)-2,5,8,11-tetraoxadodecane are preferably used. These bisoxetane compounds may be used alone or in combination of two or more kinds.
- The bisoxetane compound represented by the formula (1) can be prepared by, for example, a method of reacting a sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane and a diol compound in the presence of a base (Japanese Patent Laid-Open No.
2000-302774 2000-319577 - The amount of the bisoxetane compound used cannot be absolutely determined since the amount varies with the kind of the compound used. The bisoxetane compound is usually used in an amount of preferably from 0.001 to 3% by mol, more preferably from 0.01 to 2% by mol, and still more preferably from 0.1 to 1% by mol, based on the total amount of the water-soluble ethylenically unsaturated monomer used to obtain the water-absorbent resin precursor, from the viewpoint of sufficiently increasing the crosslinking density in a surface vicinity of the water-absorbent resin thereby enhancing the properties such as the water-absorption capacity under load, and from the viewpoint of preventing excess crosslinking reactions thereby enhancing the water-retention capacity.
- In the present invention, it is possible to mix a known crosslinking agent in addition to the above-mentioned bisoxetane compound during the post-crosslinking reaction. The post-crosslinking agent including the bisoxetane compound is preferably used by dissolving in a solvent. The type of solvent includes water; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol; ketones such as acetone, and methyl ethyl ketone; and the like. These solvents may be used alone or in combination of two or more kinds. Among them, water and alcohols are preferably used.
- The above-mentioned solvent is used in an amount of preferably from 1 to 50 parts by mass, more preferably from 1 to 40 parts by mass, and still more preferably from 5 to 40 parts by mass, based on 100 parts by mass of the water-absorbent resin precursor.
- The timing for adding the post-crosslinking agent including the bisoxetane compound is not particularly limited, as long as the timing is after the water-absorbent resin precursor is obtained by polymerizing the water-soluble ethylenically unsaturated monomer. For example, a method including the step of adding the post-crosslinking agent to a water-containing gel of the water-absorbent resin precursor after polymerization, a method including the steps of adjusting water in the the water-absorbent resin precursor by dehydrating and drying a water-containing gel after polymerization, and thereafter adding the post-crosslinking agent thereto, a method including the step of adding the post-crosslinking agent to the water-absorbent resin precursor obtained by dehydrating and drying a water-containing gel after polymerization, together with an appropriate amount of water (here, the water-absorbent resin precursor may be used in a state of dispersing in a petroleum hydrocarbon medium, as occasion demands), and the like are included. The post-crosslinking agent is added to the water-absorbent resin precursor, and thereafter, for example, the post-crosslinking reaction is carried out while distilling off water and/or a petroleum hydrocarbon medium by heating, whereby the water-absorbent resin of the present invention can be obtained.
- The water content of the water-absorbent resin precursor immediately prior to adding the post-crosslinking agent is preferably 65% by mass or less, more preferably from 1 to 50% by mass or less, still more preferably from 5 to 50% by mass or less, and still more preferably from 5 to 33% by mass or less. Here, in the present invention, the "water content" is the value determined by the determination method described below.
- By adding a post-crosslinking agent including the bisoxetane compound to the water-absorbent resin precursor, mixing them and thereafter heating, a surface vicinity of the water-absorbent resin precursor can be crosslinked. The temperature for the above-mentioned heating is preferably from 50° to 200°C, and more preferably from 80° to 180°C, from the viewpoint of rapidly and evenly crosslinking a surface vicinity of the water-absorbent resin thereby enhancing the properties such as the water-retention capacity and the water-absorption capacity under load, and from the viewpoint of preventing decomposition or degradation of the water-absorbent resin. In addition, the reaction time is preferably 0.1 to 5 hours, and preferably 0.5 to 4 hours.
- Also, it is preferably used to add a reaction aid in order to keep the reaction temperature low and shortening the reaction time during the post-crosslinking reaction. As the reaction aid, proton acid and Lewis acid are preferably used. For example, inorganic acids such as sulfuric acid, phosphoric acid and hydrochloric acid; organic acids such as citric acid, glyoxylic acid, glycolic acid, glutaric acid, cinnamic acid, succinic acid, and lactic acid; and the like are preferably used. Among them, phosphoric acid and lactic acid are more preferably used.
- The amount of the reaction aid used cannot be absolutely determined since the amount varies with the kind of the compound used, reaction conditions and the like. The reaction aid is desirably 0.0001 to 5-fold the amount of the bisoxetane compound on the molar basis.
- An additive such as a lubricant, a deodorizing agent or an antimicrobial agent may be further added to the water-absorbent resin of the present invention depending upon its purpose.
- The water-absorbent resin obtained by the production method of the present invention has a retention capacity of physiological saline of 30 g/g or more, an absorption capacity of physiological saline under a load of 2.07 kPa of 15 mL/g or more, and has a water-soluble substance of 20% by mass or less. Since the water-absorbent resin obtained by the method of the present invention is excellent in properties such as water-retention capacity, and water-absorption capacity under load, and also gives consideration to safety of the water-absorbent resin by reducing water-soluble substance, the water-absorbent resin can be preferably used in hygienic materials.
- Here, retention capacity of physiological saline, absorption capacity of physiological saline under load of 2.07 kPa, and water-soluble substance are the values determined according to the determination method described as set forth below.
- The water-absorbent resin of the present invention has a retention capacity of physiological saline of preferably 30 g/g or more, more preferably 35 g/g or more, even more preferably 40 g/g or more, and even more preferably from 40 to 70 g/g, from the viewpoint of, upon being used in a hygienic material, increasing absorption capacity and lowering the amount of re-wet of liquid.
- In addition, the water-absorbent resin of the present invention has an absorption capacity of physiological saline under a load of 2.07 kPa of preferably 15 mL/g or more, more preferably 17 mL/g or more, even more preferably 20 mL/g or more, and even more preferably from 20 to 45 mL/g, from the viewpoint of, upon being used as a hygienic material, lowering the amount of re-wet of liquid in a case where pressure is applied to the hygienic material after liquid absorption.
- The water-absorbent resin of the present invention has a water-soluble substance of preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of, upon being used in a hygienic material, preventing adhesion of the slimy liquid to the skin.
- As above-mentioned, a water-absorbent resin precursor is obtained by polymerizing a water-soluble ethylenically unsaturated monomer, and thereafter, a bisoxetane compound is added thereto as a crosslinking agent, to carry out a post-crosslinking reaction, whereby a water-absorbent resin which is excellent in properties such as water-retention capacity, and water-absorption capacity under load, while giving consideration to safety for the human body by reducing water-soluble substance, can be obtained.
- The reason why the water-absorbent resin having excellent properties and reduced water-soluble substance as above-mentioned can be obtained is not clear. Although not wanting to be limited by theory, the reason can be presumed as follows. Briefly, it is considered that the reason is due to the fact that, a water-absorbent resin precursor is reacted in the presence of a bisoxetane compound as a post-crosslinking agent, whereby a reaction of a carboxyl group and an oxetane group in the water-absorbent resin proceeds in an appropriate rate, so that a surface vicinity of the water-absorbent resin can be evenly crosslinked in a high crosslinking density. In particular, it is considered that the bisoxetane compound described herein has a glycol chain in its molecule thereby being excellent in water solubility, so that the compound is excellent in an even dispersion upon being added to the water-absorbent resin precursor, or in compatibility with the precursor, thereby making it possible to crosslink the surface vicinity more evenly.
- The present invention will be further specifically described hereinbelow by means of Synthesis Examples, Production Examples, Examples and Comparative Examples, without intending to limit the scope of the present invention to these Synthesis Examples, Production Examples and Examples.
- The evaluations of the water-absorbent resin obtained in each of Examples and Comparative Examples were made in accordance with the following procedures.
- The amount 2.0 g of water-absorbent resin were weighed in a cotton bag (Cottonbroad No. 60, width 100 mm × length 200 mm), and placed in a 500 ml-beaker. Physiological saline (0.9% by mass aqueous solution of sodium chloride, hereinafter referred to the same) was poured into the cotton bag in an amount of 500 g at one time, and the physiological saline was dispersed so as not to generate an unswollen lump of the water-absorbent resin. The upper part of the cotton bag was tied up with a rubber band, and the cotton bag was allowed to stand for 1 hour, to sufficiently swell the water-absorbent resin. The cotton bag was dehydrated for 1 minute with a dehydrator (manufactured by Kokusan Enshinki Co., Ltd., product number: H-122) set to have a centrifugal force of 167G. The mass Wa (g) of the cotton bag containing swollen gels after the dehydration was determined. The same procedures were carried out without adding water-absorbent resin, and the empty mass Wb (g) of the cotton bag upon wetting was determined. The water-retention capacity was calculated from the following formula.
- The absorption capacity of physiological saline of water-absorbent resin under load of 2.07 kPa was determined using an apparatus X of which outline constitution was shown in
Figure 1 . - The apparatus X shown in
Figure 1 comprises aburet section 1, alead tube 2, a measuringboard 3, and ameasuring section 4 placed on the measuringboard 3. To theburet section 1 are connected arubber plug 14 on the top of aburet 10, and anair introduction tube 11 and acock 12 at the bottom portion of theburet 10, and further, theair introduction tube 11 has acock 13 at the end. Thelead tube 2 is attached between theburet section 1 and the measuringboard 3. Thelead tube 2 has an inner diameter of 6 mm. A hole of a diameter of 2 mm is made at the central section of the measuringboard 3, and thelead tube 2 is connected thereto. The measuringsection 4 has acylinder 40, anylon mesh 41 adhered to the bottom part of thecylinder 40, and aweight 42. Thecylinder 40 has an inner diameter of 2.0 cm. Thenylon mesh 41 has an opening of 200 mesh (75 µm), and is configured so as a predetermined amount of the water-absorbent resin 5 to be evenly spread over thenylon mesh 41. Theweight 42 has a diameter of 1.9 cm and a mass of 59.8 g. Thisweight 42 is placed on the water-absorbent resin 5, so that a 2.07 kPa load can be applied to the water-absorbent resin 5. - In the apparatus X having the configuration above-mentioned, first, the
cock 12 and thecock 13 at theburet section 1 are closed, and a physiological saline adjusted to 25°C is poured from the top of theburet 10 and the top of the buret is plugged with therubber plug 14. Thereafter, thecock 12 and thecock 13 at theburet section 1 are opened. Next, the height of the measuringboard 3 is adjusted so that the end of thelead tube 2 in the central section of the measuringboard 3 and an air introduction port of theair introduction tube 11 are at the same height. - On the other hand, 0.10 g of the water-
absorbent resin 5 is evenly spread over thenylon mesh 41 in thecylinder 40, and theweight 42 is placed on the water-absorbent resin 5. The measuringsection 4 is placed so that its central section is in alignment with a lead tube port in the central section of the measuringboard 3. - The volume reduction of the physiological saline in the
buret 10, i.e., the volume of the physiological saline absorbed by the water-absorbent resin 5, Wc (ml), is continuously read off, from a time point where the water-absorbent resin 5 started absorbing water. The absorption capacity of physiological saline under load of the water-absorbent resin 5 after 60 minutes passed from a time point of starting water absorption was obtained by the following formula. - The amount 500±0.1 g of physiological saline was weighed out in a 500 ml-beaker. A magnetic stirrer bar (8 mm φ × 30 mm, ringless) was placed therein, and the beaker was placed on a magnetic stirrer (HS-30D, manufactured by iuchi). Subsequently, the magnetic stirrer bar was adjusted so as to rotate at a rate of 600 r/min. In addition, a bottom of a vortex generated by rotation of the magnetic stirrer bar was adjusted so as to be near an upper portion of the magnetic stirrer bar.
- Next, 2.0±0.002 g of water-absorbent resin was quickly poured between the center of vortex in the beaker and the side of the beaker and dispersed therein, and the mixture was stirred for 3 hours. The aqueous dispersion of the water-absorbent resin after stirring for 3 hours was filtered with a standard sieve (opening of sieve: 75 µm), and the resulting filtrate was further subjected to suction filtration using a Kiriyama type funnel (Filter Paper No. 6).
- The amount 80 ± 0.0005 g of the resulting filtrate was weighed out in a 100 ml-beaker adjusted to a constant weight. The filtrate was dried with a forced convection oven (FV-320, manufactured by ADVANTEC) set at an internal temperature of 140°C until a constant weight was attained, and a mass Wd (g) of the solid content of the filtrate was determined.
-
- JIS standard sieves, a sieve having an opening of 850 µm, a sieve having an opening of 600 µm, a sieve having an opening of 425 µm, a sieve having an opening of 300 µm, a sieve having an opening of 150 µm, a sieve having an opening of 75 µm, and a receiving tray were combined in order from the top. About 100 g of the water-absorbent resin was placed on an uppermost sieve, and shaken for 20 minutes with a rotating and tapping shaker machine.
- Next, the relationships between the opening of the sieve and an integral of a mass percentage remaining on the sieve were plotted on a logarithmic probability paper by calculating the mass of the water-absorbent resin particles remaining on each sieve as a mass percentage to an entire amount, and accumulating the mass percentages in order, starting from those having smaller particle diameters. A particle diameter corresponding to a 50% cumulative mass percentage is defined as an average particle diameter by joining the plots on the probability paper in a straight line.
- The amount 2.0 g of the water-absorbent resin (water-absorbent resin precursor) was precisely weighed out (Wg (g)) in an aluminum foil case (No. 8) of which constant weight (Wf (g)) was previously attained. The above sample was dried for 2 hours with a forced convection oven (manufactured by ADVANTEC) set at an internal temperature of 105°C. Thereafter, the dried sample was allowed to be cooled in a desiccator, and a mass Wh (g) after drying was determined. The drying loss (water content) of the water-absorbent resin (water-absorbent resin precursor) was calculated from the following formula.
- A 1-liter four-neck flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube was charged with 44.1 g (0.38 mol) of 3-ethyl-3-hydroxymethyloxetane, 44.6 g (0.44 mol) of triethylamine and 220 g of toluene. The contents were externally cooled in an ice-water bath until the internal temperature was 5°C under a nitrogen gas atmosphere. Next, 45.8 g (0.4 mol) of methanesulfonyl chloride was added dropwise so as the internal temperature not to exceed 10°C. Thereafter, the temperature was allowed to return to room temperature, and the contents were further stirred for 2 hours. After the reaction, the resultant triethylamine hydrochloride was filtered off, and washed with a small amount of toluene, to give a reaction filtrate.
- The above reaction filtrate was returned to the flask, and 6.4 g (0.02 mol) of tetra-n-butylammonium bromide as a catalyst and 13.7 g (0.22 mol) of ethylene glycol were added thereto. The contents were heated to the internal temperature of 60°C, and thereafter 12 g (0.3 mol) of sodium hydroxide in a pellet form was added under stirring over a period of 1 hour. Subsequently, the contents were reacted at the same temperature for 2 hours, and the internal temperature was then raised to 70°C and the reaction was allowed to proceed for 5 hours. After the reaction, 60 g of ion-exchange water was added in order to dissolve the resultant salt and to remove an excess amount of alkali, followed by cooling the flask. The reaction solution was transferred to a separatory funnel to allow phase separation, and the resulting organic layer was distilled in a reduced-distillation apparatus at an oil bath temperature of 140°C and a reduced pressure degree of 3 mmHg, to give 34.1 g of a
target 1,6-bis(3-ethyloxetane-3-yl)-2,5-dioxahexane (0.13 mol, yield:68%, purity 86%). Here, the purity was determined from the peak area ratio in the chart obtained from gas chromatography. - A 2-liter four-neck flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube was charged with 672 g (8.4 mol) of 50% by mass aqueous solution of sodium hydroxide, 25.5 g (0.075 mol) of tetra-n-butylammonium hydrogensulfate, and 330 g of n-hexane. The contents were heated in an oil bath until the internal temperature was 65°C under a nitrogen gas atmosphere. Next, 58.1 g (0.5 mol) of 3-ethyl-3-hydroxymethyloxetane was added dropwise, and stirred at the same temperature for 30 minutes. Next, 93.5 g (0.5 mol) of 1,2-bis(2-chloroethoxy)ethane was added dropwise at the same temperature over 1 hour, and thereafter the reaction was allowed to proceed for another 8 hours. After the reaction, and 450 g of ion-exchange water was added in order to dissolve the resultant salt and to remove an excess amount of alkali , followed by cooling the flask. The reaction solution was transferred to a separatory funnel to allow phase separation, and the resulting organic layer was distilled in a reduced-distillation apparatus at an oil bath temperature of 250°C and a reduced pressure degree of 3 mmHg, to give 38.1 g of a
target 1,12-bis(3-ethyloxetane-3-yl)-2,5,8,11-tetraoxadodecane (0.11 mol, yield:22%, purity 94%). Here, the purity was determined from the peak area ratio in the chart obtained from gas chromatography. - A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube and a stirring blade was prepared. This flask was charged with 340 g of n-heptane, and 0.92 g of a sucrose stearate having an HLB of 3 (manufactured by Mitsubishi-Kagaku Foods Corporation, Ryoto sugar ester S-370) and 0.92 g of a maleic anhydride-modified ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Inc., Hi-wax 1105A) were added thereto. The temperature was raised to 80°C while stirring, to dissolve the surfactant, and thereafter the solution was cooled to 50°C.
- On the other hand, a 500 ml-Erlenmeyer flask was charged with 92 g (1.02 mol) of an 80% by mass aqueous solution of acrylic acid, and 146.0 g of a 21% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.11 g (0.41 mmol) of potassium persulfate and 9.2 mg (0.06 mmol) of N,N'-methylenebisacrylamide were added thereto to dissolve, to prepare an aqueous monomer solution for the first step.
- The entire amount of this aqueous monomer solution for the first step was added to the above separable flask, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was immersed in a water bath at 70°C to raise the temperature, and the first-step polymerization was carried out for 1 hour and then cooled to a room temperature, to give a polymerization slurry of the first step.
- On the other hand, an another 500 ml-Erlenmeyer flask was charged with 128.8 g (1.43 mol) of an 80% by mass aqueous solution of acrylic acid, and 159.0 g of a 27% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.16 g (0.59 mmol) of potassium persulfate and 12.9 mg (0.08 mmol) of N,N'-methylenebisacrylamide were added thereto to dissolve, to prepare an aqueous monomer solution for the second step.
- The entire amount of this aqueous monomer solution for the second step was added to the above slurry after polymerization, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was again immersed in a water bath at 70°C to raise the temperature, and the second-step polymerization was carried out.
- After the second-step polymerization, the reaction mixture was heated with an oil bath at 125°C, whereby only water was removed from the azeotropic mixture of n-heptane and water. Further, n-heptane in the internal of the system was removed by distillation, to give 237.5 g of the water-absorbent resin precursor (A1), which is an aggregate of spherical particles and has an average particle size of 359µm. The water-absorbent resin precursor at this point had a drying loss (water content) of 7.1% by mass.
- A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, was charged with 50 g of the water-absorbent resin precursor obtained in Production Example 1 (A1) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 0.52 mol) and 80 g of n-heptane. The internal temperature was raised to 80°C. Hereafter, 8.0 g of water was added thereto, and the mixture was kept at the same temperature for 10 minutes (the water content of the water-absorbent resin precursor: 19.9% by mass).
- Thereafter, 5.0 g of a 10% by mass aqueous solution of 1,6-bis(3-ethyloxetane-3-yl)-2,5-dioxahexane (1.9 mmol), obtained by Synthesis Example 1, was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 2 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 2.3% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, was charged with 50 g of the water-absorbent resin precursor obtained in Production Example 1 (A1) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 0.52 mol) and 80 g of n-heptane. The internal temperature was raised to 80°C. Thereafter, 8.0 g of water was added thereto, and the mixture was kept at the same temperature for 10 minutes (the water content of the water-absorbent resin precursor: 19.9% by mass).
- Thereafter, 5.0 g of a 10% by mass aqueous solution of 1,12-bis(3-ethyloxetane-3-yl)-2,5,8,11-tetraoxadodecane (1.4 mmol), obtained by Synthesis Example 2, was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 3 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 2.1% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, was charged with 50 g of the water-absorbent resin precursor obtained in Production Example 1 (A1) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 0.52 mol) and 80 g of n-heptane. The internal temperature was raised to 80°C. Thereafter, 3.5 g of water was added thereto, and the mixture was kept at the same temperature for 10 minutes (the water content of the water-absorbent resin precursor: 13.2% by mass).
- Thereafter, 5.0 g of a 10% by mass aqueous solution of 1,6-bis(3-ethyloxetane-3-yl)-2,5-dioxahexane (1.9 mmol), obtained by Synthesis Example 1, was added thereto as a post-crosslinking agent, and 5.0 g of a 10% by mass aqueous solution of a phosphoric acid (5.1 mmol) as a reaction aid were added thereto and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 1 hour while drying, to give the water-absorbent resin. The drying loss (water content) was 3.4% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- A cylindrical rotund bottomed separable flask having an internal diameter of 110 mm, equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, was charged with 50 g of water-absorbent resin precursor obtained in Production Example 1 (A1) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 0.52 mol) and 80 g of n-heptane. The internal temperature was raised to 80°C. Thereafter, 3.5 g of water was added thereto, and the mixture was kept at the same temperature for 10 minutes (the water content of the water-absorbent resin precursor: 13.2% by mass).
- Thereafter, 5.0 g of a 10% by mass aqueous solution of 1,12-bis(3-ethyloxetane-3-yl)-2,5,8,11-tetraoxadodecane (1.4 mmol), obtained by Synthesis Example 2, as a post-crosslinking agent, and 5.0 g of a 10% by mass aqueous solution of a phosphoric acid (5.1 mmol) as a reaction aid were added thereto and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 1 hour while drying, to give the water-absorbent resin. The drying loss (water content) was 3.4% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube and a stirring blade was prepared. This flask was charged with 340 g of n-heptane, and 0.92 g of a sucrose stearate having an HLB of 3 (manufactured by Mitsubishi-Kagaku Foods Corporation, Ryoto sugar ester S-370) and 0.92 g of a maleic anhydride-modified ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Inc., Hi-wax 1105A) were added thereto. The temperature was raised to 80°C while stirring, to dissolve the surfactant, and thereafter the solution was cooled to 50°C.
- On the other hand, a 500 ml-Erlenmeyer flask was charged with 92 g (1.02 mol) of an 80% by mass aqueous solution of acrylic acid, and 146.0 g of a 21% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.11 g (0.41 mmol) of potassium persulfate as a radical polymerization initiator and 9.2 mg (0.06 mmol) of N,N'-methylenebisacrylamide as an internal-crosslinking agent were added thereto to dissolve, to prepare an aqueous monomer solution for the first step.
- The entire amount of this aqueous monomer solution for the first step was added to the above separable flask, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was immersed in a water bath at 70°C to raise the temperature, and the first-step polymerization was carried out and then cooled to a room temperature, to give a polymerization slurry of the first step.
- On the other hand, an another 500 ml-Erlenmeyer flask was charged with 128.8 g (1.43 mol) of an 80% by mass aqueous solution of acrylic acid, and 159.0 g of a 27% by mass aqueous sodium hydroxide was added dropwise thereto with cooling from external to neutralize 75% by mol. Thereafter, 0.16 g (0.59 mmol) of potassium persulfate as a radical polymerization initiator and 12.9 mg (0.08 mmol) of N,N'-methylenebisacrylamide as an internal-crosslinking agent were added thereto to dissolve, to prepare an aqueous monomer solution for the second step.
- The entire amount of this aqueous monomer solution for the second step was added to the above slurry after polymerization, and the internal of the system was sufficiently replaced with nitrogen. Thereafter, the flask was again immersed in a water bath at 70°C to raise the temperature, and the second-step polymerization was carried out.
- After the second-step polymerization, the temperature of the reaction solution was raised in an oil bath at 125°C, and 260 g of water was removed outside the system while refluxing n-heptane by azeotropic distillation of n-heptane and water, to give 266 g of the water-absorbent resin (A2) (water content: 18.3% by mass.). To the resulting water-absorbent resin (A2) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 2.45 mol), a 10% by mass aqueous solution of 23.8 g of a 10% by mass aqueous solution of 1,6-bis(3-ethyloxetane-3-yl)-2,5-dioxahexane (9.2 mmol), obtained by Synthesis Example 1, as a post-crosslinking agent, and 16.6 g of a 10% by mass aqueous solution of a lactic acid (18.4 mmol) as a reaction aid were added thereto. This reaction solution was heated using an oil bath at 175°C, and water and n-heptane were removed by distillation. The post-crosslinking reaction was carried out for 1 hour while drying, to give 238 g of the water-absorbent resin. The drying loss (water content) was 2.4% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- For the water-absorbent resin (A1) obtained in Production Example 1, the physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, was charged with 50 g of the water-absorbent resin precursor obtained in Production Example 1 (A1) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 0.52 mol) and 80 g of n-heptane.
- The internal temperature was raised to 80°C. Thereafter, 5.0 g of a 10% by mass aqueous solution of 1,4-butanediol (5.5 mmol) was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 2 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 2.0% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, was charged with 50 g of the water-absorbent resin precursor obtained in Production Example 1 (A1) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 0.52 mol) and 80 g of n-heptane.
- The internal temperature was raised to 80°C. Thereafter, 5.0 g of a 10% by mass aqueous solution of 3-methyl-3-oxetanemethanol (4.9 mmol) was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 2 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 3.2% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
- A cylindrical round bottomed separable flask having an internal diameter of 110 mm, equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, was charged with 50 g of the water-absorbent resin precursor obtained in Production Example 1 (A1) (Theoretical amount of the water-soluble ethylenically unsaturated monomer used to obtain the precursor: 0.52 mol) and 80 g of n-heptane.
- The internal temperature was raised to 80°C. Thereafter, 16.7 g of a 3% by mass aqueous solution of di[1-ethyl(3-oxetanyl)]methyl ether (2.3 mmol) was added thereto as a post-crosslinking agent, and mixed. This mixture was heated using an oil bath at 175°C, and water and n-heptane of the resulting mixture were removed by distillation. The post-crosslinking reaction was carried out for 2 hours while drying, to give the water-absorbent resin. The drying loss (water content) was 2.2% by mass. The physical properties of the water-absorbent resin were determined by the methods described above and the results were shown in Table 1.
-
[Table 1] Temperature Time Retention Capacity of Physiological Saline Absorption Capacity of Physiological Saline under Load of 2.07 kPa Water-soluble Substance [°C] [hr] [g/g] [ml/g] [% by mass] Ex.1 175 2 45 21 14 Ex. 2 175 3 46 20 16 Ex. 3 175 1 40 25 12 Ex. 4 175 1 44 21 15 Ex. 5 175 1 43 22 13 Comp. Ex. 1 - - 66 6 27 Comp. Ex. 2 175 2 44 22 22 Comp. Ex. 3 175 2 42 24 24 Comp. Ex. 4 175 2 47 11 18 - It can be seen from the results shown in Table 1 that the water-absorbent resin obtained in each Example has an excellent water-retention capacity and water-absorption capacity under load, and a low water-soluble substance.
- The water-absorbent resin obtained by the method for producing a water-absorbent resin of the present invention is excellent in properties such as water-retention capacity, and water-absorption capacity under load, and also gives consideration to safety of the water-absorbent resin by reducing water-soluble substance. Therefore, the water-absorbent resin of the present invention can be preferably used, for example, in hygienic materials such as disposable diaper, incontinence pad and sanitary napkin, in particular, in disposable diaper.
Claims (4)
- A method for producing a water-absorbent resin, characterized by adding a bisoxetane compound represented by the following general formula (1):
to a water-absorbent resin precursor obtainable by polymerizing water-soluble ethylenically unsaturated monomers, and subjecting the components to a post-crosslinking reaction while heating. - The method for producing a water-absorbent resin according to claim 1, wherein the amount of the bisoxetane compound is from 0.001 to 3% by mol, based on a total amount of the water-soluble ethylenically unsaturated monomer used for obtaining a water-absorbent resin precursor.
- The method for producing a water-absorbent resin according to claim 1 or 2, characterized in that phosphoric acid or lactic acid is added as a reaction aid during the post-crosslinking reaction.
- A water-absorbent resin obtainable by the method as defined in any one of claims 1 to 3, characterized in that the water-absorbent resin has a retention capacity of physiological saline of 30 g/g or more, an absorption capacity of physiological saline under a load of 2.07 kPa of 15 ml/g or more, and a water-soluble substance of 20% by mass or less.
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JP2007193371 | 2007-07-25 | ||
PCT/JP2008/061992 WO2009013978A1 (en) | 2007-07-25 | 2008-07-02 | Method for production of water-absorbable resin, and water-absorbable resin produced by the method |
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US (1) | US20100197491A1 (en) |
EP (1) | EP2177566B1 (en) |
JP (1) | JP5551438B2 (en) |
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US9221030B2 (en) | 2011-03-28 | 2015-12-29 | Sumitomo Seika Chemicals Co., Ltd. | Method for producing water-absorbent resin |
JPWO2017200085A1 (en) * | 2016-05-20 | 2019-04-18 | Sdpグローバル株式会社 | Water-absorbent resin particles, method for producing the same, absorbent comprising the same and absorbent article |
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EP1199327A2 (en) * | 2000-10-20 | 2002-04-24 | Nippon Shokubai Co., Ltd. | Water-absorbing agent and process for producing the same |
WO2006033477A1 (en) * | 2004-09-24 | 2006-03-30 | Nippon Shokubai Co., Ltd. | Particulate water-absorbing agent containing water-absorbent resin as a main component |
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JP3434028B2 (en) | 1994-07-20 | 2003-08-04 | 株式会社日本触媒 | Method for modifying water absorbent resin, water absorbent and water absorbent resin composition |
JP4860019B2 (en) | 1998-11-05 | 2012-01-25 | 株式会社日本触媒 | Water-absorbing agent and production method and use thereof |
JP3800858B2 (en) * | 1999-04-26 | 2006-07-26 | 宇部興産株式会社 | Process for producing bisoxetane ether compounds |
JP4168530B2 (en) | 1999-05-07 | 2008-10-22 | 宇部興産株式会社 | UV curable composition for coating, coating material obtained therefrom and method for producing the same |
JP2005258460A (en) * | 1999-09-17 | 2005-09-22 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the same, process for producing resist pattern, and process for producing printed circuit board |
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JP4054185B2 (en) * | 2000-10-20 | 2008-02-27 | 株式会社日本触媒 | Water-absorbing agent and method for producing water-absorbing agent |
CN1277583C (en) * | 2001-06-08 | 2006-10-04 | 株式会社日本触媒 | Water-absorbing agent, its production and sanitary material |
JP4067330B2 (en) * | 2002-04-18 | 2008-03-26 | 株式会社日本触媒 | Water-absorbing agent mainly composed of highly water-absorbing resin having a crosslinked structure, production method thereof, and sanitary material using the same |
JP2004233635A (en) * | 2003-01-30 | 2004-08-19 | Konica Minolta Holdings Inc | Method for manufacturing heat developable material |
WO2004083284A1 (en) * | 2003-03-17 | 2004-09-30 | Sumitomo Seika Chemicals Co., Ltd. | Process for production of water-absorbing resin particles |
WO2004101628A1 (en) * | 2003-05-13 | 2004-11-25 | Sumitomo Seika Chemicals Co., Ltd. | Method for producing water-absorbing resin |
CN100436486C (en) * | 2003-12-25 | 2008-11-26 | 住友精化株式会社 | Method for producing water-absorbing resin |
WO2006109552A1 (en) * | 2005-04-12 | 2006-10-19 | Konica Minolta Medical & Graphic, Inc. | Actinic ray hardenable composition, actinic ray hardenable inkjet ink, method of image forming, and inkjet recording apparatus |
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WO2006033477A1 (en) * | 2004-09-24 | 2006-03-30 | Nippon Shokubai Co., Ltd. | Particulate water-absorbing agent containing water-absorbent resin as a main component |
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Title |
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DATABASE WPI Week 200219 Thomson Scientific, London, GB; AN 2002-142501 XP002600710 & JP 2001 115006 A (UBE IND LTD) 24 April 2001 (2001-04-24) * |
DATABASE WPI Week 200425 Thomson Scientific, London, GB; AN 2004-260003 XP002600723 & JP 2003 313446 A (NIPPON SHOKUBAI CO LTD) 6 November 2003 (2003-11-06) * |
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WO2009013978A1 (en) | 2009-01-29 |
US20100197491A1 (en) | 2010-08-05 |
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JP5551438B2 (en) | 2014-07-16 |
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